CN106189027B - A kind of biological brake - Google Patents

A kind of biological brake Download PDF

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CN106189027B
CN106189027B CN201610562194.3A CN201610562194A CN106189027B CN 106189027 B CN106189027 B CN 106189027B CN 201610562194 A CN201610562194 A CN 201610562194A CN 106189027 B CN106189027 B CN 106189027B
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egc
ppy
elastin laminin
brake
composite
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CN106189027A (en
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邢孟秋
商海涛
魏泓
蒋坤
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Wuhan Hualianke Biotechnology Co ltd
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Qianhai Shenzhen Jin Zhuo Biotechnology Co Ltd
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08L2205/00—Polymer mixtures characterised by other features
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    • C08L2312/00—Crosslinking

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Abstract

The present invention relates to a kind of remote biometric brake, the biological brake includes elastin laminin composite crystal glue Iron oxide magnetic nanoparticles composite, the elastin laminin composite crystal glue Iron oxide magnetic nanoparticles composite includes elastin laminin composite crystal glue and the Iron oxide magnetic nanoparticles being carried on the brilliant glue, wherein the elastin laminin composite crystal glue includes elastin laminin, gelatin and CNT.

Description

A kind of biological brake
The Application No. 201610395996.X submitted this application claims on June 3rd, 2016 Chinese patent application it is excellent First weigh.
Technical field
The present invention relates to a kind of remote biometric brake.
Background technology
Hydrogel has extensive use in organizational engineering and biological electronics[1].At present, to their extensive concern Concentrate on high-performance and New function, such as stimulation-response performance for Drug controlled release[2], for biological electronics or life The conductibility of thing sensor[3], conductibility and elasticity for heart tissue engineering[4,5], presser sensor conductibility and for electricity The self-healing of sub- skin[6], the matrix separated for oil/water[7], the magnetic response for biological brake[8].Although being passed with excellent The function hydrogel of the property led or magnetic responsiveness energy is widely used, but still has some by flexible, elasticity and response in some fields Limited caused by sensitiveness is not enough, such as high flexibility electronic equipment, organic pressure sensitive sensors and response actuator.Their faces Face the similar challenge for being combined together highly conductive property or magnetic response property with high flexibility and elasticity.
It was recently reported that some syringes-injectable macropore flexible netted electronic equipment, reflects the bioelectronics of manufacture Equipment without operation transplantation prospect[9], but the huge electronic equipments of the prefabricated 3D of syringe-injectable are not reported so far.Although report The brilliant glue of some macropores such as alginate, gelatin, chitosan and hyalomitome acid crystals glue has high flexibility and syringe-can note Penetrating property, they all do not have conductibility[10,11], because introducing CNT (CNT) and polypyrrole (PPY) etc. has conduction Property rigid components will strengthen hydrogel hardness but reduce their flexibility simultaneously[12]。
In pressure sensitive sensors field, several method, such as hollow-spheroid compression resistance film sensing have been developed Device[13], nanowires of gold compression resistance film sensors[14], dimethyl silicone polymer (PDMS)/CNT (CNT) nanometer sheet sensing Device[15]With nano wire matrix film sensors[16], but these technologies run into Similar Problems：Complicated manufacturing process, high cost and have The conductibility of limit.In addition, they are the 2D films for electric dermal application rather than the huge pressure sensings of 3D for some environment Device.Some conductibility hydrogels are reported, but these hydrogels do not conduct the good elasticity of compression/resistance and pressure-responsive Property is combined together[17,18]。
In addition, it was recently reported that the magnetic hydrogel of external magnetic field can be responded quickly to, it delivers medicine/thin by remote boot server Born of the same parents, it is in about 38A/m2Magnetic field gradient under can reach about 70% deformation[19].Also manufacture good conductibility and magnetic sound 3D graphenes/iron oxide the aeroge that should be combined together is used for the potential application of soft actuator or micro switch, and it is in 1.2T magnetic There is 52.3% radial strain under field intensity[20].However, as little as 0.2T to 3T modest magnetic field is more to can be used for common face Bed environment, andLow-field MRI be commonly applied to MRI[21], therefore in actual applications remote boot server need it is more flexible and Sensitive magnetic response hydrogel.
Therefore, there is still a need for it is a kind of can by conductibility or magnetic responsiveness with high flexibility and elasticity are good is combined together New composite.
The content of the invention
The first aspect of the present invention provide a kind of elastin laminin composite crystal glue (EGC), it include elastin laminin, gelatin and CNT.Wherein, " brilliant glue " refers to the continuous gel-type vehicle with interconnected macropore.
In one embodiment of the invention, the elastin laminin of elastin laminin composite crystal glue including 30-60 parts by weight, The gelatin of 30-80 parts by weight and the CNT of 10-80 parts by weight.In one embodiment, the ratio of elastin laminin and gelatin For 30/70 to 70/30, such as 30/70 to 50/50.The elastin laminin may be selected from Elastin peptide, tropoelastin or digestion bullet Property albumen.In one embodiment, elastin laminin and gelatin pass through methacrylated modification.In one embodiment, Methacrylated reagent is methacrylic anhydride.In one embodiment, the elastin laminin is grafted for methacrylate Elastin laminin.In one embodiment, the gelatin is methacrylate grafted gelatin.In one embodiment, it is described EGC also includes the stabilizer of stabilizer, such as 30-80 parts by weight.The stabilizer can be amphipathic copolymer, for example polyoxy second The amphipathic copolymer of alkene-polyoxypropylene polyoxyethylene (PEO-PPO-PEO) three block, such as F-127-DA.In an embodiment In, the stabilizer passes through acryliated modification.In one embodiment, propylene acidizing reagent is acryloyl chloride.In the present invention An embodiment in, elastin laminin composite crystal glue includes elastin laminin, the gelatin of 35 parts by weight, 17.5 weights of 15 parts by weight Measure the CNT of part and the stabilizer of 17.5 parts by weight.
The SEM morphology of EGC hydrogels show (Fig. 1 (e1)) similar to cellular macroporous structure and with 60~ 130 μm of pore-size distribution and the interconnectivity higher than 99%, it can allow deformation and Quick drainage, and by CNT (5mg/ ML, ultimate density) it is embedded in the mesh grid of substrate layer (as come from Fig. 1 (e2)).
Present invention also offers a kind of method for preparing EGC, methods described includes：
(a) elastin laminin, gelatin, CNT and stabilizer are mixed in aqueous；
(b) polymerization initiator is added into said mixture at low temperature, mixture is crosslinked；
(c) solidify at low temperature products therefrom in step (b), to form EGC.
In one embodiment of the invention, the step of the inventive method in (a), by the elasticity of 30-60 parts by weight Albumen, the gelatin of 30-80 parts by weight, the stabilizer of the CNT of 10-80 parts by weight and 30-80 parts by weight are mixed in aqueous Close.In one embodiment, elastin laminin and gelatin pass through methacrylated modification.In one embodiment, methyl Propylene acidizing reagent is methacrylic anhydride.In one embodiment, the elastin laminin is methacrylate grafted elastomeric Albumen.In one embodiment, the gelatin is methacrylate grafted gelatin.In one embodiment, the stabilizer It is amphipathic copolymer, such as amphipathic copolymer of PEO-PPO-PEO three blocks, such as F-127-DA.In one embodiment, The stabilizer passes through acryliated modification.In one embodiment, the polymerization initiator includes ammonium persulfate (APS), For example, APS and tetramethylethylenediamine (TEMED).In one embodiment, the solidification of step (c) continues 1-24h, for example 16h。
In one embodiment, step (a) is to carry out at low temperature, such as is carried out at a temperature of 0-15 DEG C.One In individual embodiment, step (b) is carried out at 0-15 DEG C.In one embodiment, step (c) is carried out at -30-0 DEG C, excellent - 20 DEG C of choosing.
The second aspect of the present invention provides a kind of brilliant glue composite, and it includes the polypyrrole of EGC and load thereon (PPY).In one embodiment, EGC and PPY weight ratio about 1:0.15-0.7.
In one embodiment, scattered polypyrrole aggregation (EGC-PPY-FD) is loaded with EGC.This is scattered poly- Pyrroles's aggregation can be deposited by Quick cross-linking and polypyrrole aggregation is deposited on EGC.In one embodiment, quickly Crosslinking deposition is to trigger pyrrole monomer to gather by the way that the pyrrole monomer in solution is absorbed on EGC, and by ammonium persulfate (APS) Merge quick in situ formation on EGC, to form the polypyrrole aggregation (EGC-PPY-FD) being supported on EGC.In a reality Apply in scheme, the concentration of the pyrrole monomer in solution is 3mg/mL-18mg/mL, such as 6.7mg/mL-13.4mg/mL, such as 6.7mg/mL.In one embodiment, in EGC-PPY-FD, EGC and PPY weight ratio about 1:0.15-0.30, for example 1:0.23-0.29, such as 1:0.26.
In another embodiment, continuous polypyrrole network structure is formed in the network structure of the EGC.Specifically For, rigid PPY compositions form the second network (EGC-PPY-SA) on soft support.Now, form with soft-hard co-continuous The brilliant glue composite of network structure.In one embodiment, the composite is the then slow aging by Quick cross-linking Formed in the network structure of the brilliant glue formed by continuous polypyrrole network structure.In one embodiment, it is described Composite is, by the way that pyrrole monomer is absorbed on EGC, and to add Fe (NO3)3To trigger pyrroles to be crosslinked, then make residue not The pyrrole monomer of polymerization is by Fe (NO3)3Slow oxidation polymerization is with the formation contiguous network structure in the network structure of the brilliant glue. In one embodiment, the concentration of the pyrrole monomer in solution is 3mg/mL-18mg/mL, such as 6.7mg/mL-13.4mg/ ML, such as 13.4mg/mL.In one embodiment, in EGC-PPY-SA, EGC and PPY weight ratio about 1:0.32- 0.70, such as 1:0.32-0.50, such as 1:0.38.
In one embodiment, the EGC-PPY-FD formed pore-size distribution is 50~140 μm, and it is similar to EGC Pore-size distribution, and EGC-PPY-SA pore-size distribution be 20~60 μm.
The scattered PPY aggregations of EGC loads show highly flexible and syringe-injectable property and medium biography The property led.On the other hand, when rigid PPY compositions form the second network on soft support, with soft-hard co-continuous network structure Up to 50.1 ± 2.9S/ brilliant glue shows the outstanding high resiliency that can bear up to 97.5% compression strain and strained 90% simultaneously under Cm protrusion conductibility and good presser sensor conductibility.
Present invention also offers the method for preparing EGC-PPY-FD, it includes EGC being soaked in pyrroles's aqueous solution, and adds Enter polymerization initiator (such as APS), so that pyrrole monomer polymerize, and in-situ deposition is on EGC supporting structure, to form EGC- PPY-FD.In one embodiment, the reaction is carried out at low temperature, for example, carried out at 0-15 DEG C.In a reality Apply in scheme, the concentration of the pyrrole monomer in solution is 3mg/mL-18mg/mL, such as 6.7mg/mL-13.4mg/mL, such as 6.7mg/mL。
Present invention also offers the method for preparing EGC-PPY-SA, it includes EGC being soaked in pyrroles's aqueous solution, and adds Enter Fe (NO3)3To trigger pyrroles to be crosslinked, then make remaining unpolymerized pyrrole monomer by Fe (NO3)3Slow oxidation polymerization with Contiguous network structure is formed in EGC network structure.Generally, Fe (NO are added3)3It is at low temperature, for example to trigger pyrroles's crosslinking Carried out at 0-15 DEG C.Aging (such as Fe (NO3)3Slow oxidation) 4 hours to 3 days can be continued at room temperature, preferably 8 hours to 3 My god, and preferably 8 hours, 16 hours, 1 day, 2 days and 3 days.
The third aspect of the present invention provides a kind of brilliant glue composite (EGC-IONP), and it includes EGC and is carried on EGC On Iron oxide magnetic nanoparticles (IONP).In one embodiment, EGC-IONP includes the elastic egg of 30-60 parts by weight In vain, the gelatin of 30-80 parts by weight, the CNT of 10-80 parts by weight, the Iron oxide magnetic nanoparticles of 30-120 parts by weight and The stabilizer of 30-80 parts by weight.In one embodiment, elastin laminins of the EGC-IONP comprising 50 parts by weight, 50 parts by weight Gelatin, the Iron oxide magnetic nanoparticles of the CNT of 20 parts by weight and 120 parts by weight.In one embodiment, it also includes The polypyrrole of polypyrrole, e.g., from about 30-80 parts by weight.In one embodiment, the PPY is used and quick friendship like above Connection is deposited and is deposited in EGC-IONP (EGC-IONP-PPY-FD).
Present invention also offers a kind of method for preparing EGC-IONP, methods described includes：
(a) elastin laminin, gelatin, CNT, Iron oxide magnetic nanoparticles and stabilizer are mixed in aqueous；
(b) polymerization initiator is added into said mixture at low temperature, mixture is crosslinked；
(c) solidify at low temperature products therefrom in step (b), to form the composite.
, can be by the elastin laminin of 30-60 parts by weight, the gelatin of 30-80 parts by weight, 10-80 the step of this method in (a) The stabilizer of the CNTs of parts by weight, the Iron oxide magnetic nanoparticles of 30-120 parts by weight and 30-80 parts by weight is water-soluble Mixed in liquid.In one embodiment, elastin laminin and gelatin pass through methacrylated modification.In an embodiment In, methacrylated reagent is methacrylic anhydride.In one embodiment, the elastin laminin connects for methacrylate Branch elastin laminin.In one embodiment, the gelatin is methacrylate grafted gelatin.In one embodiment, should Stabilizer is amphipathic copolymer, for example the amphipathic copolymer of PEO-PPO-PEO three blocks, such as F-127-DA.In an implementation In scheme, the stabilizer passes through acryliated modification.In one embodiment, the polymerization initiator includes ammonium persulfate (APS), such as APS and TEMED.In one embodiment, the solidification of step (c) continues 1-24h, such as 16h.
In one embodiment, step (a) and step (b) are carried out at 0-15 DEG C respectively.In one embodiment, Step (c) is carried out at -30-0 DEG C, preferably -20 DEG C.
Present invention also offers a kind of method for preparing EGC-IONP-PPY-FD, it passes through PPY described above quick Crosslinking is deposited and is deposited in EGC-IONP, to form EGC-IONP-PPY-FD.
It is used for the invention further relates to EGC, EGC-PPY-FD, EGC-PPY-SA, EGC-IONP and EGC-IONP-PPY-FD The purposes of oil/water separation, the manufacture of artificial heart, biology sensor, remote-controlled robot or biological brake etc..
The invention further relates to a kind of biological brake, the biological brake includes EGC-IONP composites.In a reality Apply in scheme, the biological brake is made up of EGC-IONP composites.In one embodiment, the EGC-IONP is combined Material is, for example, EGC-IONP-PPY-FD.In the present invention, the biological brake can be control electric current loop opened/closed Device.
In one embodiment, EGC-IONP composites used are prepared by the following method：
(a) elastin laminin, gelatin, CNT, Iron oxide magnetic nanoparticles and stabilizer are mixed in aqueous；
(b) polymerization initiator is added into said mixture at low temperature, mixture is crosslinked；
(c) solidify at low temperature products therefrom in step (b), to form the elastin laminin composite crystal glue-iron oxide Magnetic nanoparticle composite；And
Optionally, the composite obtained by step (c) is soaked in pyrroles's aqueous solution, and adds the second polymerization and triggered Agent, so that pyrrole monomer polymerize, and in-situ deposition is carried on described be combined on the supporting structure of the composite to be formed Scattered polypyrrole aggregation on material.
The EGC-IONP composites of the application by using with flexible EGC, and mix with magnetic IONP and Conductive PPY, is formd while having the elastomeric material of flexible, electric conductivity and magnetic.By applying magnetic field, Ke Yigai Become the elastomeric material.For example, under conventional weak electric field, such as in about 38A/m2Application magnetic field gradient under, the application's EGC-IONP composites can realize 30-180 ° of bending.By using this mode, it can be made to be used to control remote circuit Switch.The method of this circuit for remotely controlling can be widely applied to the remote circuit control that operator is difficult to reach.Or, this The method of kind circuit for remotely controlling can be used for operator and be difficult to manually operated or be not suitable for manually operated circuit, or micro- electricity Road.Further, since employing biomaterial, this biological brake is also bio-compatible.
In one embodiment, the biological brake can be made into the bar shaped brake for being suitable for circuit control.The system One end of dynamic device be may connect in circuit, and the other end is stayed open.When applying conventional low-intensity magnetic field, by controlling magnetic field Change, the biological brake of the bar shaped can be made to deform, and then make another contact of its other end and circuit, make circuit Close and connect.
In one embodiment, the biological brake can be used as circuit changing switch.When magnetic field application thereon when, should Biological brake is transformed into closure state from open mode, or is transformed into open mode from closure state.
In one embodiment, the invention discloses a kind of circuit, the circuit includes power supply, indicator and is used as circuit Switch the biological brake of switch, the biological brake includes EGC-IONP composites.In one embodiment, the power supply Can be the conventional power supply in this area, such as battery, battery pack, alternating current and other conventional power supplys.The indicator can this The conventional indicator in field, such as bulb, light emitting diode etc..
The invention further relates to a kind of supercompression electric conductivity and magnetic response gel robot, it includes main body and is connected to it On three to eight side arms composition.In one embodiment, the remote-controlled robot is artificial octopus robot.In an implementation In scheme, the material of main part is EGC-IONP composites, such as EGC-IONP-PPY-FD.In one embodiment, it is described Main body can be polyurethane sponge.Or, the main body can be magnetic hydrogel, such as EGC-IONP composites.In an implementation In scheme, the artificial octopus robot can be controlled and be operated using magnetic field.
The invention further relates to a kind of oil/water isolation medium, it includes EGC-PPY composites as described above.At one In embodiment, the oil/water isolation medium is EGC-PPY-FD.The invention further relates to a kind of chromatogram separated for oil/water Oil/water isolation medium in post, wherein chromatographic column includes EGC-PPY composites as described above.
Brief description of the drawings
Fig. 1 is showing the figure of the quick elasticity, shape memory property and their form of the brilliant glue of EGC-PPY.(a1) Bear EGC (30) (elastin laminin/gelatin=30/70)-PPY-SA before compression；(a2) EGC (30)-PPY- of compression is born SA；(a3) the quick resilience of EGC (30)-PPY-SA after revocation compression.(b1) drain water EGC (30)-PPY-SA without extensive Multiple deformation；(b2) EGC (the 30)-PPY-SA for draining water is immersed in the water again；(b3) EGC (30)-PPY-SA recovers shape. (c1) EGC (30)-PPY-FD hydrogels of deformation are taken out；(c2) EGC (30)-PPY-FD hydrogels；(c3) EGC of deformation (30) the shape memory sexual behaviour that-PPY-FD hydrogels slowly recover in water.(d1) there is the EGC of " U " or " M " shape (30)-PPY-SA hydrogels；(d2) EGC (30)-PPY-SA hydrogels after deforming；(d3) returned in water before deformation EGC (30)-PPY-SA hydrogels of " U " or " M " shape.(e1) SEM image (95 times of magnifying power) of EGC (30) hydrogel； (e2) show that CNT is embedded in the SEM image (23000 times of magnifying power) of EGC (30) hydrogel of substrate layer.(f1) by quick The SEM image (190 times of magnifying power) of the EGC hydrogels (EGC (30)-PPY-FD) of the PPY coatings of crosslinking；(f2) it is display PPY SEM image (magnifying power 11000) of the dispersed distribution of aggregates of nanoparticles on EGC (30) hydrogel.(g1) by slow The SEM image (800 times of magnifying power) of the EGC hydrogels (EGC (30)-PPY-SA) of the PPY coatings of aging, (g2) shows that PPY receives Rice grain deposits the image (13000 times of magnifying power) of the good PPY networks of the development formed on support.(h1) followed for 10 times Ring, under 80% compression strain, EGC (30)-PPY-SA shape memory strains change of the fixed rate with cycle-index；(h2) EGC (30)-PPY-SA shape recovery ratio with cycle-index change.
Fig. 2 is showing the figure of the engineering properties of the brilliant glue of EGC.(a) under 20mm/min speed, with 80% strain EGC (30), EGC (30)-PPY-FD, EGC (30)-PPY-SA, elastin laminin, the compression stress of gelatin and gelatin-CNT hydrogels Strain curve.(b) in the case where 80% strains, influence of the elastin laminin/gelatin mass fraction to their mechanical strength (notes： Before reaching 80% strain, EGC (0) partial rupture).(c) under 20mm/min and (d) 200mm/min compression speed, for The load-deformation curve of EGC (30)-PPY-SA hydrogels under the strain of 100 circulations 80%.(e) it is right under 2mm/min In 5 circulations, the stress-strain cycle curve of EGC (30)-PPY-SA hydrogels under 97.5% Large strain.(f) in 24h Afterwards, under 2mm/min speed, for 5 circulations, the second compression of same sample-off-load fortune under 97.5% Large strain OK.(g) it is respectively subjected to EGC (30)-PPY-SA of 0% and 97.5% compression strain photo.
Fig. 3 is the figure of the rheological property of brilliant glue.(a)EG(30)、(b)EGC(30)、(c)EGC(30)-PPY-FD、(d) EGC (50), (e) EGC (50)-PPY-FD and (f) EGC (30)-PPY-SA hydrogels.(g1)-(g3) is that tool is figurate The injectable behavior of EGC (50)-PPY-FD conductibility hydrogels.
Fig. 4 is that conductive figure (a1)-(a3) of presser sensor shows and gradually deformed along with EGC (30)-PPY-SA, The presser sensor behavior that LED luminous intensity is gradually stepped up.(b)：(a1)-(a3) circuit is illustrated.(c1) deformation EGC (30)- PPY-SA hydrogels are used as " ON/OFF " contactor；(c2) display is by adding DD water restorable EGC (30)-PPY-SA Hydrogel switch is by circuit together with LED lights；(c3) DD water, which is used only, in display can not make LED light.(d)：(c1)-(c3) Circuit illustrate.(e) EGC (30), EG (50)-PPY-FD, EGC (50)-PPY-FD and EGC (30)-PPY-SA conductibility, lead to Cross digital conductibility tester (n=3 (positive direction) and n=3 (the negative direction)) detection of 4 probes.(f) EGC (30)-PPY-SA Apparent resistance cyclic test spectrogram (50% strain, 20mm/min).(g) EGC (30)-PPY-SA conductibility-compression strain spectrum Figure, by digital conductibility tester (n=3 (positive direction) and n=3 (the negative direction)) detection of 4 probes.
Fig. 5 is the figure of the separation of oil-in-water emulsion.(a) separation of plant oil-in-water emulsion.(b) emulsion before separating The optical microscope image of emulsion after optical microscope image and (c) separation.(d) statistical analysis (n=of droplet size 4992).(e) vegetable oil is not flowed into EGC (30)-PPY-FD hydrogels of compression, but water is flowed into the hydrogel of compression immediately.
Fig. 6 is the magnetic response behavior of the brilliant glue comprising IONP.(a) in the case where 80% strains, IONP ultimate densities are to EGC (50) influence of-IONP compressive strengths.(b) under 20mm/min speed, for 10 circulations, EGC (50)-IONP stress- Cyclic Strain curve (20mg/mL).(c) EGC (50)-IONP high flexibility and compressibility.(d) under the magnetic field of weak application, by The artificial octopus robot that EGC (50)-IONP is made.(e) the long-range conductibility of EGC (50)-IONP-PPY-FD controlled by magnetic field Biological brake.
Fig. 7 is the schematic diagram for preparing the brilliant glue of Multifunctional elastic albumen.Including high flexibility, injectable, shape memory, biography The property led, presser sensor, the brilliant glue of EGC-PPY-FD, EGC-PPY-SA and EGC-IONP-PPY of water-oil separating and magnetic response property Manufacture.
Fig. 8 is the diagram of the high resiliency mechanism of the brilliant glue of EGC-PPY-SA under compressive stress.
Fig. 9 is that 0.5mg pyrroles is used as outer target methacrylated gelatin (gelatin-MA, 12mg)1H H NMR spectroscopies.Base In gelatin-MA and pyrroles concentration, rubbing for methacrylate can be calculated by comparing the peak intensity at 5.4ppm and 5.65ppm Your amount, belongs to the proton of methacrylate, the peak intensity at 6.2ppm and 6.9ppm places is from pyrroles's external standard.Methyl in gelatin The calculated value of acrylate amount is 0.02285mol per 100g gelatin.
Figure 10 is the methacrylated elastin laminin (elastin laminin-MA, 18.8mg) of 0.5mg pyrroles1H NMR Spectrum.Concentration based on elastin laminin-MA and pyrroles, can calculate methyl-prop by comparing the peak intensity at 5.4ppm and 5.65ppm The mole of olefin(e) acid ester, belongs to the proton of methacrylate, and the peak intensity at 6.2ppm and 6.9ppm comes from pyrroles's external standard. The calculated value of methacrylate amount is 0.02285mol per 100g gelatin in gelatin.
Figure 11 is F-127 diacrylates1H H NMR spectroscopies.
Figure 12 is by CDCl3From Fe (NO3)3The pyrroles's of the residual of the slow aging reaction extraction triggered1H H NMR spectroscopies (DMSO is external standard, 0.29mg/mL).Wherein, the residual concentration of pyrroles can be calculated according to following equation：
The mole of the pyrroles of residual
=(intensity6.84ppm+ intensity6.27ppm)/4 × (intensity2.6ppm/ 6) × (0.00029/78.13) × 67.09,
Wherein, 78.13 be DMSO mole.And 67.09 be pyrroles mole.
Aliquot volume based on the reaction solution for extraction and the CDCl for NMR signs3Aliquot volume, Ke Yiji It is 96% to calculate reaction conversion ratio.
Figure 13 is by CDCl3From the pyrroles of the residual of the APS pyrroles fast deposition reaction, extractions triggered1H H NMR spectroscopies (DMSO is external standard, 0.29mg/mL).
Figure 14 is the figure of the statistical analysis in brilliant glue aperture.(a) the brilliant glue of EGC (30), average pore size, 90 ± 14 μm, (b) EGC (30)-PPY-FD, average pore size, 98 ± 19 μm, (c) EGC (30)-PPY-SA, average pore size, 39 ± 8 μm.
Figure 15 is GC (30), EGC (30)-PPY-FD and EGC (30)-PPY-SA performance map.Wherein (a) is water content, (b) it is expansion rate (volume of sample preparation is 360 μ l).Note：PPY weight is not considered when calculating expansion rate.
Figure 16 is that the frequency of the brilliant glue of EGC with the different slow aging technique times sweeps collection rheology spectrum.(a)EGC(30)- 0h, (b) EGC (30)-PPY-SA-8h, (c) EGC (30)-PPY-SA-16h, (d) EGC (30)-PPY-SA-1d, (e) EGC (30) the brilliant glue of-PPY-SA-2d and (f) EGC (30)-PPY-SA-3d.
Figure 17 is the gelatin-CNT and EGC image after 80% strain is born under speed 20mm/min.
Figure 18 is EGC (30)-PPY-SA compression-unloading cyclic stress-strain curve.(a) 50% strain, 20mm/ Min, (b) 50% are strained, 200mm/min, and (c) 70% is strained, 20mm/min, and (d) 70% is strained, 200mm/min, (e) 80% Strain, 200mm/min and (f) 80% are strained, 20mm/min.
Figure 19 is the figure of the engineering properties of the brilliant glue of control group PEG- diacrylates-elastin laminin-CNT EGC.In speed There is PEG, PEG-CNT (5mg/mL), PEG-EL (30)-CNT (5mg/mL), the PEG-EL of 80% strain under 20mm/min (30) compression stress strain curve of the brilliant glue of-CNT-PPY-FD and PEG-EL (30)-CNT-PPY-SA.
Figure 20 is that, for 100 circulations, PEG-EL (30)-CNT-PPY-SA compression-unloading Rotation permutations are bent Line, 80% strain, 20mm/min.
Figure 21 is to use the different insoluble organic solvent (density of water>1.0) EGC-PPY oleophobic property under water.(a) chlorine It is imitative, (b) dichloromethane and (c) carbon disulfide.(dyeing organic solvent by different colours).
Embodiment
In order to realize the target for being combined together high flexibility and elasticity with excellent conductive or magnetic response behavior, applicant It was found that the use of the high flexibility and elastic support of the function nano composition with high capacity amount being effective ways.Water-soluble elastin laminin (such as Elastin peptide, tropoelastin or digestion elastin laminin) is good high resiliency support candidate, but it lacks machine Tool intensity[22].However, the brilliant glue of elastin laminin is rarely employed, because its bad mechanical strength and passing through ice in freezing gel Crystalline substance forms the big pore morphology produced and even reduce further mechanical strength[10,23,24]。
Applicant has been surprisingly found that obtaining super flexible using the brilliant glue of high water soluble Elastin peptide (EGC crystalline substances glue) Support, it with gelatin, excellent and biocompatibility gelatinous mass and the CNT of high loading by being combined further strengthen[25].It is soft Property Elastin peptide and gelatin chain can form the network of rigid CNT microcells and flexibility/flexible polymer coil bridge to obtain with rigidity CNT Obtain high resiliency[26].In addition, the CNT of hydrogel middle and high concentration can form network to improve the conductibility in support[4,27]。
Then, high conductance polypyrrole nano components are supported on to obtain excellent conductibility on EGC supports, wherein PPY morphology plays key effect to the macroscopic property of brilliant glue[28].When EGC loads scattered PPY aggregations, brilliant glue is shown Highly flexible and syringe-injectable property and medium conductibility.When rigid PPY compositions form the second network on soft support When, the brilliant glue with soft-hard co-continuous network structure is shown simultaneously can bear the outstanding high resiliency of paramount 97.5% compression strain With the protrusion conductibility and good presser sensor conductibility of paramount 50.1 ± 2.9S/cm under 90% strain.
Applicant also prepares EGC-IONP and EGC-IONP-PPY with by high flexibility, sensitiveness, conduction by same procedure Property be combined together with magnetic response property, display is used as long-range and soft actuator or machine human potential.It has been found that EGC- PPY hydrogels are to be used for the ideal chromatography post that " oil-water " is separated[24]。
In this application, methacrylated Elastin peptide (elastin laminin-MA, from the hydrolysis of ox paxwax can be passed through Then it is methacrylated), methacrylated gelatin (gelatin-MA) and many wall CNT brilliant gel prepare EGC hydrogels.It is logical The amphipathic copolymer of F-127-DA polyoxyethylene-poly-oxypropylene polyoxyethylenes (PEO-PPO-PEO) three block is crossed to disperse CNT When in water, hydrophobic PPO blocks will assemble and with the interaction of CNT non covalent hydrophobic and hydrophilic PEO chains molten Extend and with gelatin-MA and elastin laminin-MA covalent bondings to form hydrogel in liquid, it will increase CNT and water-setting matrix The affinity of matter.CNT and hydrogel matrix affinity are evaluated by immersion tests of the 48h in distilled water (DD water) and passed through UV-vis is measured, and it shows>99.9%CNT is stable in hydrogel[27].Therefore, by serving as the hydrophobic PPO bags of Physical crosslinking agent The CNT microcells enclosed can form the elastomeric network (CNT preparation process) with soft elastin laminin/gelatin/PEO polymer line bridges.Branch PPY coatings on frame deposit (EGC-PPY-FD) or (2) Quick cross-linking by (1) Quick cross-linking, then slow aging (EGC- PPY-SA).In EGC-PPY-FD technique, the pyrrole monomer absorbed in EGC hydrogels is triggered, assemble, is settled out simultaneously And quick in situ absorbs on EGC supports to form scattered PPY aggregations.Quick cross-linking deposition can be carried out at low temperature, Carried out for example at 0-15 DEG C.In EGC-PPY-SA techniques, pass through insufficient amount of Fe (NO3)3Trigger pyrroles, its residue is not gathered The monomer of conjunction is used for by (NO3)3Slow oxidation polymerization is with the formation contiguous network structure on support and slow process allows PPY More intermolecular hydrogen bondings interaction between gelatin/elastin substrate[29,30].In EGC-PPY-SA techniques, quickly What crosslinking can be carried out at low temperature, such as carried out at 0-15 DEG C, aging can be carried out at room temperature.
Embodiment
Method
Experimental section
Material：Water-soluble Elastin peptide (Elastin Products Company, CB573, molecular weight be 1000 to 60000Da.These peptides include cross-linking amino acids desmosine and isodensmosine, and repeat peptide Val-Gly-Val-Ala-Pro- Gly), gelatin (type A, Sigma Aldrich).Every other chemicals be purchased from Sigma Aldrich, and directly use and It is not further purified.
Embodiment 1：The synthesis of methacrylate grafted gelatin (gelatin-MA).
According to document disclosed above[25], methacrylic acid ester group is introduced to gelatin by being combined with primary amine group Skeleton.Briefly say, 2g type A gelatin is dissolved in 20mL PBSs (1 ×) at 50 DEG C, then by 2mL methyl Acrylic anhydride (MA) stirs added to gelatin solution and together 1hr at 50 DEG C.After reacting, 100mL PBS is fallen Enter with dilute solution in reactor, and at 40 DEG C, use 10kDa MWCO dialysis tubings DD H2O by gelatin solution dialyse 5 My god.Finally, white porosity foam is reclaimed at -45 DEG C by desivac, yield is 85%.
Embodiment 2：The synthesis of methacrylate grafted elastomeric albumen (elastin laminin-MA).
The preparation of methacrylate grafted elastomeric albumen (elastin laminin-MA) is similar to the program of foregoing description, but Entirely react and occur in ice bath.Briefly, in ice bath, 2g elastin laminin is dissolved in 20mL PBSs (1 ×) In, 2mL methacrylic anhydride (MA) is then stirred into 8hr added to elastin laminin solution and in ice bath together.Anti- Ying Hou, at 4 DEG C, uses 1000Da MWCO dialysis tubings DD H2O dialyses solution 48h, and is freezed at -45 DEG C, yield For 40%.
Embodiment 3：The synthesis of F-127- diacrylates.
Closed by using the acrylated F-127 of acryloyl chloride (poly- (the propane diols)-b- PEGs of PEG-b-) Into F-127- diacrylates.Briefly, in ice bath, by 2.54g (0.2mmol) F-127 and 0.061g triethylamine (0.6mmol) is dissolved in 20mL anhydrous methylene chlorides and advertises degassing 20min by nitrogen.Then, under nitrogen protection, will 0.05mL acryloyl chlorides (0.6mmol) are slowly injected in solution.Solution is stirred into 24hr, and reaction temperature is risen into room naturally Temperature.After the reaction, solvent is removed by rotary evaporation, and dialysed 3 days with DD water by the dialysis tubing of the MWCO with 3.5kDa Reclaimed by product purification, and by desivac.White solid is reclaimed, yield is 2.06g (81%).
NMR is characterized.Owned on Bruker Avance 300MHz NMR spectrometers1H NMR are tested, and by relaxation Delay (relaxation delay, d1) is set to 2 seconds.Sample is dissolved in by D with 10mg/mL concentration2O.A large amount of pyrroles are added Add in gelatin-MA NMR solution and elastin laminin-MA is used to quantify what is be grafted on gelatin or elastin laminin as external standard The amount of methacrylate.All NMR datas are referring to accompanying drawing.
Embodiment 4：EGC preparation.
It is previously prepared in DD H2The 50mg/mL storages of the 50mg/mL stock solutions and elastin laminin-MA of gelatin-MA in O Standby solution, and stored using preceding in refrigerator.By 100mg multi-walled carbon nanotubes (MWCNT), 100mg F-127-DA and 10mL DD H2O is added in 50mL plastic tubes and in ice bath by the probe sonication ultrasonically treated 4h of ripple homogenizer, and is using preceding place Manage other 1h.In typical prepare, in ice bath, by 30 μ l elastin laminin-MA (50mg/mL), 70 μ l gelatin-MA (50mg/mL), 75 μ l DD H2O and 175 μ l CNT solution are sufficiently mixed.Then, the 5 μ l 10%TEMED aqueous solution is added With 5 μ l 200mg/mL ammonium persulfates (APS) aqueous solution and mixed in succession in ice bath, and solution is aspirated to tool with pipettor (reverse 1.5mL EP tanks or 96- orifice plates) and good seal in the mould of body, and store 16hr to be solidificated at -20 DEG C.Then, Hydrogel (is expressed as EGC (30), elastin laminin/gelatin=30/70) wash several times thoroughly to remove desalination using DD water.With shifting Solution produced above 90 μ l of liquid device absorption is managed to 1.5mL EP and solidification prepares injectable sample at -20 DEG C.Preparation has 720 μ l sample solutions of the compression-unloading cyclic test for being used for 97.5% strain of same concentrations and ratio.
According to three groups of lyophilized samples (3 × 360 μ l each group), the actual weight of EGC crystalline substances glue (coming from 360 μ l solution) is 7.1±0.1mg.CNT and water-setting are detected by UV-vis spectrum (Ultrospec 4300pro, UV/ visible spectrophotometer) The affinity of gel matrix.Using DD water by the sample cyclic washing of selection several times to remove any salt and impurity from reaction.So Afterwards, respectively by those sample (volumes：360 μ l) 48h in 2mL DD water is immersed in, and water keeps colourless after 48h, collects it 1mL aliquot samples be used for UV visible light analysis, using CNT dilute solution (1mg/mL, 0.1mg/mL, 0.01mg/mL and 0.001mg/mL) as standard.After 48h, it is retained in more than 99.9%CNT in hydrogel.
The brilliant glue (EGC (50)) of EGC that elastin laminin/gelatin=50/50 is prepared for using identical method.
Embodiment 5：EGC-PPY-FD preparation.
EGC (30) hydrogel (7.1mg) prepared in embodiment 4 is immersed in 4mL 6.7mg/mL (0.1mol/L) pyrrole Cough up in the aqueous solution, and 1mL APS (89.6mg/mL, 0.4mmol) aqueous solution is poured into chromium solution (actual pyrrole in ice bath Concentration is coughed up for 0.08mol/L).After 30min, reaction is stopped and hydrogel is thoroughly washed using DD water.It is lyophilized according to three groups Sample (3 × 360 μ l each group), the actual weight (coming from 360 μ l solution) of EGC-PPY-FD crystalline substance glue is 9.0 ± 0.2mg.Water-setting PPY load capacity on glue is 5.2 ± 0.4mg/mL.
Embodiment 6：EGC-PPY-SA preparation.
EGC (30) hydrogel (7.1mg) prepared in embodiment 4 is immersed in 2mL 13.4mg/mL (0.2mol/L) pyrrole Cough up in the aqueous solution, and by the Fe (NO of equivalent in ice bath3)3The aqueous solution (0.2mol/L, 80.8mg/mL) is poured into chromium solution. Solution is sufficiently mixed and hydrogel is compressed and discharged several times so that chromium solution is absorbed into the support of hydrogel.By solution 3d is stored at room temperature, and EGC-PPY hydrogels are removed, and uses DD H2O is thoroughly washed.The sample tool used in Figure 16 There are different soak times, including 8h, 16h, 1d, 2d and 3d.According to three groups of lyophilized samples (3 × 360 μ l each group), EGC- The actual weight (coming from 360 μ l solution) of PPY-SA (3d) crystalline substance glue is 9.8 ± 0.4mg.PPY load capacity on hydrogel is 7.4 ±1.2mg/mL.The affinity of PPY and hydrogel matrix is evaluated by the same procedure for CNT, and after 48h> 99.9%PPY is retained in matrix.
Embodiment 7：The preparation of IONP nano particles.
By FeCl in round-bottomed flask3(0.81g, 5mmol) and FeCl2·4H2O (0.5g, 2.5mmol) is dissolved in 10mL DD Sealed in water and by rubber spacer cap.Solution is advertised 20min thoroughly to remove air by nitrogen.In another flask In, 20mL 2M ammonia aqueous solutions are deaerated by same procedure, and is stirred at room temperature under the high stir speed (S.S.)s of 750rpm.So Afterwards, under nitrogen protection, iron salt solutions are transferred in ammonia spirit by 10mL syringes.After 1h, reaction is stopped simultaneously Black solid is collected by bar magnet, using water by its cyclic washing thoroughly to remove ammonia and salt.It is moist, by black gains It is transferred in 50mL centrifuge tubes and adds DD water to obtain 5mL aqueous mixtures altogether, and adds 0.2g F-127- diacrylates Ester.In ice bath, by probe sonication ripple homogenizer by the ultrasonically treated 2h of mixture, then 0.1mL aliquot samples are transferred to It is dried overnight in EP pipes and under vacuum drying chamber.Dry weight based on product, calculates IONP concentration (yield：0.64g).Will be another Outer 0.44g F-127- diacrylates are added in pipe and add extra 0.33mL DD water to reach 120mg/mL's IONP/F-127 concentration.Before use, by the ultrasonically treated other 10h of solution in ice bath.
Embodiment 8：EGC-IONP, EGC-IONP-PPY-FD and biological brake preparation.
EGC-IONP preparation is similar with the brilliant glue of EGC.In typical prepare, in ice bath, by 100 μ l elastic egg - MA (50mg/mL), 100 μ l gelatin-MA (50mg/mL), 200 μ l CNT solution (10mg/mL) and 200 μ l IONP are molten in vain Liquid (60mg/mL) is sufficiently mixed, then, adds the 10 μ l 10%TEMED aqueous solution and 10 μ l 200mg/mL ammonium persulfates (APS) aqueous solution and mix, and drawn solution into 1mL syringe cylinders and good seal in succession in ice bath with pipettor, be It is solidificated at -20 DEG C and stores 16hr.Can be with different scales but same ratio prepares sample.Then, using DD water by hydrogel Wash several times thoroughly to remove desalination.Hydrogel is immersed in 13.6mg/mL (0.2mol/L) pyrroles's aqueous solution, and in ice bath 2mL APS (44.8mg/mL) aqueous solution is poured into solution, the time is 20min, and the EGC of acquisition is thoroughly washed using DD water (50) the brilliant glue of-IONP-PPY-FD.4 EGC (50)-IONP hydrogels (about 2cm length) are adhered to by superglue extremely a piece of Polyurethane sponge prepares artificial octopus robot.
In addition, the brilliant glue of EGC (50)-IONP-PPY-FD made above is made to the biological brake of strip, and should Biological brake is connected to including battery, in the simple circuit of bulb, wherein biological brake one end is connected with circuit, and separately One end is stayed open.When biological brake is opened, the bulb is not lighted.And state magnetic when the biological brake is applied with outside When being closed in the presence of, the bulb is lighted.It for details, reference can be made to Fig. 6 (e) photo and schematic diagram.
In Fig. 6 (a), 30mg/mL and 40mg/mL is prepared most by using 90mg/mL the and 120mg/mLIONP aqueous solution The brilliant glue of the IONP of final concentration, is stablized by the F-127- diacrylates of same concentrations.Pass through the same procedure for CNT The affinity of IONP and hydrogel matrix is evaluated, and after 48h>99.9%IONP is retained in matrix.
The method being described as follows according to sample of the invention made above is analyzed.And retouch referring to the drawings Beneficial effects of the present invention are stated.
The conversion ratio of the gentle slow aging deposition of PPY fast depositions.
Outer target is used as by using DMSO1The pyrroles remained after H NMR detection reactions calculates conversion ratio.Because pyrroles exists There is limited solubility in water, but it is solvable using a large amount of organic solvents of such as ether, chloroform.It can be extracted by organic solvent Unreacted pyrroles characterizes for NMR.For slow aging reaction, respectively by 6.9 μ l (6.7mg) pyrroles in two EP pipes With 40.4mg Fe (NO3)3It is dissolved in 0.5mL D2O, and two solution are mixed into 4h and at room temperature altogether in ice bath Store 3d.The transparent supernatants of 0.5mL are transferred to another EP pipes, and use 0.3mL chloroform-d (CDCl3) wash 5 times to extract Take unreacted pyrroles.Take out 750 μ L aliquot samples and with as the outer μ l DMSO/CDCl of target 103Solution (22mg DMSO/ 1mL CDCl3) mix to implement1H NMR are characterized.For fast deposition reaction, 6.9 μ l (6.7mg) pyrroles will be contained in ice bath 1mL D2O and 250 μ l APS/D2O solution (89.6mg/mL) mixes 30min.Black PPY aggregations suspend in the solution, lead to Cross the syringe filtering aaerosol solution for being equipped with 0.45 μm of PDFE filter disc.0.5mL clear solution is transferred to another EP pipes And pass through 0.3mL CDCl3Extraction 5 times.Take out 750 μ L aliquot samples and with as the outer μ l DMSO/CDCl of target 103Solution (22mg DMSO/1mL CDCl3) mix to implement1H NMR are characterized.
SEM is characterized.
Hydrogel sample is freezed first, is then loaded on metal sample container to sputter the thin layer for coating gold for table Levy.Embodiment is characterized in JEOL-5900 SEM, uses 20eV operating voltage.Pass through image J softwares The aperture information of statistical analysis crystalline substance glue.
Compression test and cyclic test.
According to such scheme, the water with disk geometry (4~5mm height, 8mm diameters) is prepared in a mold in advance Gel sample.Under 20mm/min speed, implement compression test until 80% compression strain.Be equipped with a pair of compression plates and Implement compression cyclic test on the universal tensile testing machine (Instron 5965) of 500N load elements.Before the test, in compression Drip a drop water on platform, and the hydrogel sample selected is respectively subjected to 50%, 70% or 80% compression strain, Ran Hou Discharged under 20mm/min or 200mm/min constant rate of speed to 0%, repeated 100 times to detect compression performance and hydrogel Recovery.For the cyclic test with 97.5% maximum strain, height of specimen is respectively 9.8mm (mutually same with 9.1mm Product, but have some permanent deformations), and compression speed is 2mm/min.
Shape memory sexual behaviour.
EGC (30)-PPY-SA hydrogels of initial length with 10mm are used to measure.The initial gage length table of sample It is shown as L1.By sample compression to 80% strain under speed 20mm/min, and the gauge length compressed is L2.Sample is kept The 1min under the strain, and thoroughly absorption on paper handkerchief, then makes sample not have any load time to be 5min to the water extruded, The fixed gauge length of measurement is used as L3.Then, sample is immersed in water is used to be hydrated 5min again, and measures recovery Gauge length is used as L4.Those gauge lengths are measured by the clearance distance of two compression plates, by data round numbers to three small Number (mm) (passes through instrument automatic measurement L2, and clearance distance manual measurement L is adjusted by using exact position knob1、L3And L4, And actual minimum step is 0.003~0.005mm).Shape memory fixed rate and recovery rate are calculated according to following equation.
Maximum compression is strained：εm=(L1–L2)/L1× 100%
Fixed strain：εu=(L1–L3)/L1× 100%
Overstrain：εp=(L1–L3)/L1× 100%
Strain fixed rate：Rf=εu/εm× 100%
Strain recovery rate：Rr=(εm-εp)/εm× 100%
Rheological charactristicses.
At 25 DEG C, find to carry out all streams on compound rheological instrument in TA using the steel parallel-plate of 8mm diameter geometries Become and learn oscillation experiment.In vibration-frequency experimentation, sample is set to bear to accelerate to 200rad/s shearing slowly from 0.1rad/s Speed, with 0.5% constant strain.
Conductivity measurement.
Under 0.1 μ A to 100mA current range, pass through the ST-2258C numerals with linear probe (2.0mm intervals) 4- test instrument probes (Suzhou Jingge Electrical Co., Ltd.) detect the sheet resistance of hydrogel sample.In inspection Before survey, it is necessary to by all samples cyclic washing to remove the initiator of residual.Conductibility can be calculated by the ρ of equation σ=1/. Detect each sample under 70% compression strain, and calculate the average result of three values detected under positive current and in negative current The average result of three data of lower acquisition.Detected under 10%, 30%, 50%, 70% and 90% different compression strains with The data of 4g meters.
The resistance detection of pressure correlation.
Pressure-responsive conductibility, including Instron compression test platforms, high sensitivity are detected on the platform built indoors Digital multimeter and its related software, conduction copper cash and insulating tape.Discharged by sample compression and under speed 20mm/min, directly To 50% maximum strain.
Plant oil-in-water emulsion is separated.
96 orifice plates using the diameter with about 6.5mm as mould prepare sample, and program is same as described above.In dress Carry after PPY, brilliant glue laminated is reduced in 1mL syringe cylinders (outlet diameter is 2mm).By mixing 0.5mL vegetable oil and 9.5mL DD water prepares oil-in-water emulsion, and ultrasonically treated 10mins together.Pass through the aperture of image J software statistics credit crystallization glue Information.By 5 separation detection flows on phase isomorphous glue, each 0.8mL emulsions flow through brilliant glue (2mm diameter exits), and Before reuse, brilliant glue is washed in the vessel comprising DD water.
Material EGC, EGC-PPY-FD, EGC-PPY-SA, EGC-IONP, the EGC- being related in description referring to the drawings IONP-PPY-FD is prepared using the specific method described in above example, and is prepared into according to the particular content of experiment Corresponding shape.Wherein EGC (30) and EGC (50) represent material elastase/gelatin=30/70 or 50/50 respectively.
Reference picture 1
In order to obtain shape memory property, hydrogel should have (i) macropore spongy architecture to allow water freely to flow Enter/flow out, highly polar and (iii) that (ii) is used for water absorption is used for the favorable elasticity that shape is recovered[31].In the present invention, by In EGC-PPY-FD and EGC-PPY-SA macroporous structure and PPY it is highly polar, two kinds of EGC-PPY hydrogels show good bullet Property and shape memory sexual behaviour.The SEM forms of EGC hydrogels show (Fig. 1 (e1)) similar to honeycomb sample macroporous structure and Pore-size distribution with 60~130 μm and the interconnectivity higher than 99%, it can allow deformation and Quick drainage, and will CNT (5mg/mL, ultimate density) is embedded in substrate layer, such as comes from Fig. 1 (e2) mesh grid.After PPY coating, EGC (30)-PPY-FD and EGC (30) both-PPY-SA keep the macroporous structure similar with EGC (30) (Fig. 1 (f1) and (g1)), But EGC (30)-PPY-FD pore-size distribution is 50~140 μm, similar to the brilliant glue of EGC, and the distribution of the latter is drop dramatically to 20 ~60 μm, show to have accumulated more PPY in EGC (30)-PPY-SA.Fig. 1 (f2) and (g2) show that PPY nano particles gather respectively What deposition was formed in the dispersed distribution or support of collective develops good PPY networks.The formation of the good PPY networks of development is by flowing Change frequency of oscillation sweeps collection experiment (rheology oscillation-frequency sweeping experiment) and enters one Step confirms.In addition, with the increase of the slow ageing times of PPY, storage modulus substantially increases, and slow deposition two days it Afterwards, storage modulus G ', often higher than loss modulus G " without intersecting, shows at high shear rates without big in frequency range Scale allosteric rearrangement and EGC (30)-PPY dynamic mechanical properties are dominated by the rigid networks of PPY, and form soft-hard doubly-linked Continuous structure (Figure 16).
In addition, (a1)-(a3) in reference picture 1, when EGC (30)-PPY-SA cylinders bear compression stress, macropore support becomes Shape and expressed water is to discharge stress, while absorbing water when cancelling stress and recovering immediately, as shown in Figure 1a.Can from Fig. 1 b To find out, when going water removal, EGC (30)-PPY-SA (being prepared using same method) of deformation is lost its elasticity and protected Deformation is held, but when reusing water, recovers its original geometry structure immediately, shape memory sexual behaviour is shown.Pass through (1) single shaft Compression sample reaches 80% strain, and (2) water is absorbed water by paper handkerchief to keep deformation, and (3) remove load 5min and (4) by sample weight The new 5min that is immersed in the water is used to recover further to evaluate EGC (30)-PPY-SA shape-memory properties.10 circulations of calculating Fixed rate and strain recovery rate are strained, as being described in detail in experimental section.Due to the rigid networks of PPY, when removing load, pressure The hydrogel of contracting somewhat recovers, and fixed rate is about 88~90%.When being immersed in again in water, shape is in about 0.3 second Recover, and recovery rate is maintained at about 99% after 10 circulations, shows good shape memory (Fig. 1 (h1) and (h2) )[32].Fig. 1 c show EGC (30)-PPY-FD similar shape memory sexual behaviour, and it has slower recovery rate.It will can be somebody's turn to do EGC (30)-PPY-SA hydrogels are molded as " U " and " M " letter, water can be used by its fast quick-recovery, as shown in Figure 1 d.
Reference picture 2
In order to detect the high elastic of EGC-PPY hydrogels, compare EGC (30), EGC (30)-PPY hydrogels (EGC (30)-PPY-FD and EGC (30)-PPY-SA) and control sample, include the pressure of elastin laminin, gelatin and gelatin-CNT hydrogels Contracting performance, wherein proof resilience albumen/gelatin concentration are identical.In Fig. 2 (a), pure gelatin hydrogel has higher compressive strength, But local mechanical fracture is produced under being strained 75%.By adding CNT (5mg/mL), the machinery of gelatin-CNT composite aquogels is strong Degree is sharply increased, but compression stress diminishes.And Elastin peptide hydrogel only has 0.9kPa ultralow machine under being strained 80% Tool intensity.Therefore, introduce elastin laminin and drastically reduce the mechanical strength (elastin laminin/gelatin=30/70) of EGC (30) extremely 11.4kPa, and elastin laminin-base composite aquogel does not all have any mechanical breaking under 80% strain, even exists Rigid PPY layers and CNT compositions.With scattered PPY aggregations coating or continuous P PY networks, EGC (30)-PPY-FD and EGC (30)-PPY-SA shows 26.7kPa and 58.4kPa compressive strength without any fracture, increase by 2 respectively under being strained 80% Times or 5 times.In order to confirm that increased elasticity is attributed to Elastin peptide, examined by same procedure and use PEG- diacrylates (700) control group of gelatin is replaced.PEG crystalline substance glue shows highly flexible but mixing with less compression stress and with CNT Miscellaneous (5mg/mL ultimate density) produces fracture, but the display rubber elastic behavior (Figure 19) similar with PPY to elastin laminin.Fig. 2 (b) display elastin laminin peptide components reduce brilliant glue mechanical strength, and the EGC (70) when there is 5mg/mL CNT to a miracle Only there is 2.0 ± 0.4kPa intensity, the total concentration of its elastase/gelatin is 5mg/0.35mL.
In order that further evaluating high resiliency with fast quick-recovery and stable macropore conductibility hydrogel, followed for 100 times Ring, EGC (30)-PPY-SA crystalline substance glue bears 80% deformation under 20mm/min and 200mm/min speed respectively.200mm/ The hydrogel of min high compression rate requirement deformation can rapidly recover in 1.08s.As shown in Fig. 2 (c) and 2 (d), two should Power-strain spectrum shows similar closed curve.After 100 times circulate, 8.8% is lost and right for 20mm/min rate recoveries 13.8% is lost in 200mm/min rate recoveries, and hydrogel still keeps good shape and elasticity, shows its stability With the potential application in heart tissue engineering.Compared with low strain dynamic, the sample shows preferable stability and elastic performance, (Figure 18) is lost with less recovery.For 5 circulations, when the brilliant glue of EGC (the 30)-PPY-SA equally prepared is in 2mm/min Speed under when bearing 97.5% superelevation compression strain, when circulating first time, compressive strength jumps high to 6348.6kPa Value, shown in such as Fig. 2 (e).After 5 times circulate, the recovery loss of compressive strength is 26.8% and sample height under being strained 97.5% Degree is contracted to 8.6mm (12.2% deformation) from 9.8mm, but brilliant glue keeps overall shape without any obvious fracture, shows PPY The limited local fracture of layer.The sample being immersed in water recovers to 9.1mm, with 7.1% permanent deformation, and examines after 24h Look into the second compression cyclic test with up to 97.5% strain.Enjoyably, 97.5% strain under compressive strength recover to 6014.5kPa, and after 5 times circulate, the recovery loss of compressive strength is only 14.6%, such as shown in Fig. 2 (f).In circulation After experiment, there is sample other 0.5mm to shrink (5.5%), but leave after being soaked in water less than 0.1mm permanent deformations (< 1% permanent deformation).Show the outstanding elasticity of the brilliant glue of EGC-PPY-SA, the compression of 6.35Mpa stress offer 97.5% can be used in it Strain and brilliant glue support keeps good, only there is the limited local fracture of PPY layers of rigidity.
Reference picture 3
The detection of collection method is swept by vibration-frequency and evaluates elastin laminin-gelatin (EG (30)), EGC (EGC (30) and EGC (50)) and EGC-PPY (EGC (30)-PPY-SA, EGC (50)-PPY-FD and EGC (30)-PPY-FD) dynamic mechanical properties. According to Fig. 3 (a), with the increase of shear rate, there is intersection between storage modulus and loss modulus vestige, be reflected in high shear Long range molecular motion and extensive allosteric rearrangement and the high flexibility and injectable property that show EG (30) hydrogel under speed. Fig. 3 (b) and 3 (c) show EGC (30) supports and EGC (30)-PPY-FD rheological properties, and wherein G ' and G " substantially increases, but Despite the presence of desired rigid CNT and PPY, still there is the similar transition under high-rate of shear, show their highly flexible and can Injection behavior.Rigid components only strengthen brilliant glue, but engineering properties is still dominated by soft support.EGC (50) and EGC (50)-PPY-FD Show similar rheological behavior and be intended as EGC (30) and EGC (30)-PPY-FD, but less storage modulus.So And, for EGC (30)-PPY-SA, G ' and G ", the two almost increases an order of magnitude, but G " is always less than G ', shows EGC (30)-PPY-SA is due to rigid PPY networks forfeits injectable property.Correspondingly, EGC (50)-PPY-FD shows its injectable Shown in property, such as Fig. 3 (g).The figurate conductibility hydrogel of the tool can be injected by pin (ID 1.6mm), and very Recover its original shape soon.On the contrary, EGC (30)-PPY-SA can not be injected into, but with significantly higher modulus of elasticity and tool There is the high resiliency of quick recovery properties.
Reference picture 4
Fig. 4 (a) displays change its luminous intensity, show that EGC (30)-PPY-SA pressure is quick with hydrogel deformation, LED Feel conductibility, it can be used as potential source biomolecule sensor.In order to further show conductibility and the shape memory sexual behaviour of gel, such as Shown in Fig. 4 (c), by adding DD water, EGC (30)-PPY of deformation recovers to its original-shape, and when the water-setting recovered LED bulb is lighted during glue bridgt circuit, but pure DD water can not individually illuminate bulb.In order to further evaluate presser sensor conduction Property, EGC (30), EG (50)-PPY-FD, EGC (50)-PPY-FD and EGC (30)-PPY-SA hydrogels are provided in Fig. 4 (e) Conductibility.Under 70% compression strain, CNT mesh networks provide 0.004 ± 4.4 × 10 to EGC hydrogels-5S/cm biography The property led, however, the conductibility of EGC (50)-PPY-FD hydrogels comprising PPY and CNT rise two orders of magnitude reach 0.375 ± 0.024S/cm value.There is no CNT network structures, EG (50)-PPY-FD only has 0.00758 ± 0.00199S/cm value.Companion With the formation for developing good PPY networks, the conductibility of EGC (30)-PPY-SA hydrogels is increased significantly under being strained 70% 14.7±1.4S/cm.Because material has uneven cross section, conductibility is strain correlation, therefore is pressure correlation.Figure EGC (30)-PPY-SA of 50% compression strain real-time apparent resistance spectrum is born in 4 (f) display repeatedly, its display is circulated every time good Good strain correlation and comparable resistance.Highest resistance without strain and real time resistance is expressed as R0And R, And pass through R/R0Calculate relative resistance, it is strained to hydrogel be directly proportional and strained 50% under close to 25% initial value. According to EGC (30)-PPY-SA compressive stress strain curve, pressure sensibility (Δ R/R0Per kPa) it is about 0.086 every kPa.
Excellent elasticity and stress/strain correlation resistance show that the EGC hydrogels of PPY loads can ring for the huge pressure of 3D The good candidate of inductive sensing device[13].In Fig. 4 g provide EGC (30)-PPY-SA conductibility vs. strain spectrums, itself and it is non-linear increase Plus, for best sample, obtain the highest conductibility of 50.1 ± 2.9S/cm under being strained 90%, according to we grasp it is optimal Knowledge, its top is between current conductibility compression hydrogel[18,33]。
Reference picture 5
Such as document report, the grid or filter paper substrate of superoleophobic hydrogel coating under water are separated for oil/water[34].This The brilliant glue with intrinsic interconnecting macroporous structure and oleophobic property PPY coatings under water of invention[29,35]It can also be used for Oil-water separation and do not have There is porous support.When plant oil-in-water emulsion (5:95,v:V) injection of the brilliant glue of EGC (30)-PPY-FD filled with compression is passed through During device, only transparent water flows through brilliant glue, as shown in Figure 5 a.By the inspection of light microscope, after filtration with 1~28 μm of grain The oil droplet of degree distribution is wholly absent, as shown in Fig. 5 b~5d.The oleophobic property of the brilliant glue of Fig. 5 e displays, wherein vegetable oil cannot flow into pressure EGC (30)-PPY-FD hydrogels of contracting.Separating capacity is higher than 99% and flow can reach 404 ± 101L/hrm2(n= 5)。
Reference picture 6
EGC high flexibility and the elasticity of compression is considered, it can be the good candidate of magnetic response material, with the magnetic sound above reported Alginate-iron oxide tempering gel is answered to compare, it has 55~60kPa modulus and in about 38A/m under being strained 80%2 Application magnetic field gradient under show about 70% deformation[19].EGC (50)-iron oxide (IONP) is prepared according to embodiment 8 brilliant Glue, wherein by the Fe of 20mg/mL (ultimate density)3O4Nano particle is introduced to EGC (50), but its compression under 80% strain Intensity is only 5.1 ± 1.2kPa, and the brilliant glue with 40mg/mL IONP only has 11.8 ± 2.4kPa value, and display has The IONP of high carrying capacity high flexibility, such as Fig. 6 (a) and (b) are shown.From Fig. 6 (c), under the low-intensity magnetic field from constant bar EGC (50)-IONP (20mg/mL) magnetic hydrogel cylinder shows super flexible, and it is easily bent to 180 °, is injected in addition in 1mL In the constrained environment of device bucket, flexural deformation is restricted and light along the whole hydrogel cylinder of direction of principal axis when being put into magnetic field Minute-pressure is reduced to about 45% strain.Fig. 6 (d) shows that high flexibility and sensitive property become the simulation of the magnetic field control by applying Artificial octopus robot.
In addition, as shown in Fig. 6 (e), after coating PPY, EGC (50)-IONP-PPY-FD prepared by the application is kept High flexibility and it is flexible to 90 ° under magnetic field.And when the above-mentioned low-intensity magnetic field control of application, it acts as long-range conductibility Biological brake[20,36], the remote control opening and closing of circuit.
Therefore it may be concluded that water-soluble elastin laminin peptidyl brilliant glue macropore support load has conductive rigidity High resiliency, injectability and shape memory property and conductibility or magnetic properties can be combined together by PPY or IONP.Institute The EGC hydrogels for having PPY to coat show excellent elasticity, flexibility, shape memory the sexual behaviour conductibility related to stress.Especially Ground, when EGC supports load scattered PPY, the tool figurate conductibility hydrogel of generation show excellent flexibility with Injectable property, shows that it is potential as syringe-injectable biology sensor or biological electronics；As EGC-PPY is soft-hard The formation of co-continuous network, product shows high elastic modulus and the outstanding elasticity with fast quick-recovery, has under being strained 90% 50.1 ± 2.9S/cm excellent conductive, and 97.5% compression can be even born, show to be used for heart tissue engineering Learn the good candidate of material or presser sensor biology sensor.Magnetic response hydrogel EGC-IONP also keeps high flexibility and shown Sensitive magnetic response behavior, and can be used as biological brake.
Those skilled in the art are it is to be understood that can in any combination between each above-mentioned feature, and this group Close also within the scope of the present application.Artisan will appreciate that not departing from appended claims of the invention institute The change and retouching made in the case of the scope and spirit of the present invention of announcement, belong to the protection model of the claim of the present invention Within enclosing.
Bibliography：
[1]a)J.Elisseeff,Nat Mater 2008,7,271；b)J.L.Drury,D.J.Mooney, Biomaterials2003,24,4337；c)T.R.Hoare,D.S.Kohane,Polymer 2008,49,1993；d) D.Buenger,F.Topuz,J.Groll,Progress in Polymer Science 2012,37,1678；e)S.Ladet, L.David,A.Domard,Nature2008,452,76.
[2]A.Doring,W.Birnbaum,D.Kuckling,Chemical Society Reviews 2013,42, 7391.
[3]a)L.Pan,G.Yu,D.Zhai,H.R.Lee,W.Zhao,N.Liu,H.Wang,B.C.-K.Tee,Y.Shi, Y.Cui,Z.Bao,Proceedings of the National Academy of Sciences 2012,109,9287；b) B.C.-K.Tee,A.Chortos,A.Berndt,A.K.Nguyen,A.Tom,A.McGuire,Z.C.Lin,K.Tien,W.- G.Bae,H.Wang,P.Mei,H.-H.Chou,B.Cui,K.Deisseroth,T.N.Ng,Z.Bao,Science 2015, 350,313.
[4]S.R.Shin,S.M.Jung,M.Zalabany,K.Kim,P.Zorlutuna,S.b.Kim,M.Nikkhah, M.Khabiry,M.Azize,J.Kong,K.-t.Wan,T.Palacios,M.R.Dokmeci,H.Bae,X.Tang, A.Khademhosseini,ACS Nano 2013,7,2369.
[5]Z.Li,J.Guan,Polymers 2011,3,740.
[6]B.C.K.Tee,C.Wang,R.Allen,Z.Bao,Nat Nano 2012,7,825.
[7]Y.Si,Q.Fu,X.Wang,J.Zhu,J.Yu,G.Sun,B.Ding,ACS Nano 2015,9,3791.
[8]Y.Li,G.Huang,X.Zhang,B.Li,Y.Chen,T.Lu,T.J.Lu,F.Xu,Advanced Functional Materials 2013,23,660.
[9]a)J.Liu,T.-M.Fu,Z.Cheng,G.Hong,T.Zhou,L.Jin,M.Duvvuri,Z.Jiang, P.Kruskal,C.Xie,Z.Suo,Y.Fang,C.M.Lieber,Nat Nano 2015,10,629；b)G.Hong,T.- M.Fu,T.Zhou,T.G.Schuhmann,J.Huang,C.M.Lieber,Nano Letters 2015,15,6979.
[10]S.A.Bencherif,R.W.Sands,D.Bhatta,P.Arany,C.S.Verbeke,D.A.Edwards, D.J.Mooney,Proceedings of the National Academy of Sciences 2012,109,19590.
[11]a)S.A.Bencherif,R.Warren Sands,O.A.Ali,W.A.Li,S.A.Lewin, T.M.Braschler,T.-Y.Shih,C.S.Verbeke,D.Bhatta,G.Dranoff,D.J.Mooney,Nat Commun 2015,6；b)S.T.Koshy,T.C.Ferrante,S.A.Lewin,D.J.Mooney,Biomaterials 2014,35, 2477；c)C.D.Abueva,A.R.Padalhin,Y.-K.Min,B.-T.Lee,Journal of Biomaterials Applications 2015；d)L.Cheng,K.Ji,A.Haddad,T.-Y.Shih,G.Giatsidis,D.J.Mooney, D.P.Orgill,C.S.Nabzdyk,Journal of the American College of Surgeons 2015,221, e119.
[12]a)B.K.Satapathy,R.Weidisch,P.A.Janke,Composites Science and Technology 2007,67,867；b)K.Hu,D.D.Kulkarni,I.Choi,V.V.Tsukruk,Progress in Polymer Science 2014,39,1934.
[13]L.Pan,A.Chortos,G.Yu,Y.Wang,S.Isaacson,R.Allen,Y.Shi,R.Dauskardt, Z.Bao,Nat Commun 2014,5.
[14]S.Gong,W.Schwalb,Y.Wang,Y.Chen,Y.Tang,J.Si,B.Shirinzadeh,W.Cheng, Nature communications 2014,5.
[15]X.Wang,Y.Gu,Z.Xiong,Z.Cui,T.Zhang,Advanced Materials 2014,26, 1336.
[16]K.Takei,T.Takahashi,J.C.Ho,H.Ko,A.G.Gillies,P.W.Leu,R.S.Fearing, A.Javey,Nat Mater 2010,9,821.
[17]Y.Tai,M.Mulle,I.Aguilar Ventura,G.Lubineau,Nanoscale 2015,7, 14766.
[18]a)Y.Wang,Y.Shi,L.Pan,Y.Ding,Y.Zhao,Y.Li,Y.Shi,G.Yu,Nano Letters 2015,15,7736；X.Zhao,P.Li,B.Guo,P.X.Ma,Acta Biomaterialia 2015,26,236；b)Y.Shi, C.Ma,L.Peng,G.Yu,Advanced Functional Materials 2015,25,1219；c)Y.Shi,M.Wang, C.Ma,Y.Wang,X.Li,G.Yu,Nano Letters 2015,15,6276；d)S.Naficy,J.M.Razal, G.M.Spinks,G.G.Wallace,P.G.Whitten,Chemistry of Materials 2012,24,3425.
[19]X.Zhao,J.Kim,C.A.Cezar,N.Huebsch,K.Lee,K.Bouhadir,D.J.Mooney, Proceedings of the National Academy of Sciences 2011,108,67.
[20]X.Xu,H.Li,Q.Zhang,H.Hu,Z.Zhao,J.Li,J.Li,Y.Qiao,Y.Gogotsi,ACS Nano2015,9,3969.
[21]M.F.Reiser,W.Semmler,H.Hricak,Magnetic resonance tomography, Springer Science&Business Media,2007.
[22]a)S.G.Wise,S.M.Mithieux,A.S.Weiss,in Advances in Protein Chemistry and Structural Biology,Vol.Volume 78(Ed:M.Alexander),Academic Press,2009,1；b)J.-Y.Wang,World Scientific Publishing Co.Pte.Ltd.,Singapore 2014,13；c)Y.-N.Zhang,R.K.Avery,Q.Vallmajo-Martin,A.Assmann,A.Vegh,A.Memic, B.D.Olsen,N.Annabi,A.Khademhosseini,Advanced Functional Materials 2015,25, 4814.
[23]G.C.Yeo,B.Aghaei-Ghareh-Bolagh,E.P.Brackenreg,M.A.Hiob,P.Lee, A.S.Weiss,Advanced Healthcare Materials 2015,4,2530.
[24]A.Kumar,A.Srivastava,Nat.Protocols 2010,5,1737.
[25]J.W.Nichol,S.T.Koshy,H.Bae,C.M.Hwang,S.Yamanlar,A.Khademhosseini, Biomaterials 2010,31,5536.
[26]N.Annabi,S.R.Shin,A.Tamayol,M.Miscuglio,M.A.Bakooshli,A.Assmann, P.Mostafalu,J.-Y.Sun,S.Mithieux,L.Cheung,X.Tang,A.S.Weiss,A.Khademhosseini, Advanced Materials 2015,n/a.
[27]Y.Xiao,L.He,J.Che,Journal of Materials Chemistry 2012,22,8076.
[28]D.Ofer,R.M.Crooks,M.S.Wrighton,Journal of the American Chemical Society1990,112,7869.
[29]Y.Lu,W.He,T.Cao,H.Guo,Y.Zhang,Q.Li,Z.Shao,Y.Cui,X.Zhang, Scientific Reports 2014,4,5792.
[30]a)D.Beattie,K.H.Wong,C.Williams,L.A.Poole-Warren,T.P.Davis, C.Barner-Kowollik,M.H.Stenzel,Biomacromolecules 2006,7,1072；b)S. C.Demetgül,M.Timur,N.Carbohydrate Polymers 2010,79,908.
[31]a)R.Luo,J.Wu,N.-D.Dinh,C.-H.Chen,Advanced Functional Materials 2015,25,7272；b)H.Omidian,J.G.Rocca,K.Park,Macromolecular Bioscience 2006,6, 703.
[32]A.Lendlein,S.Kelch,Angewandte Chemie International Edition 2002, 41,2034.
[33]J.Hur,K.Im,S.W.Kim,J.Kim,D.-Y.Chung,T.-H.Kim,K.H.Jo,J.H.Hahn, Z.Bao,S.Hwang,N.Park,ACS Nano 2014,8,10066.
[34]a)Z.Xue,S.Wang,L.Lin,L.Chen,M.Liu,L.Feng,L.Jiang,Advanced Materials2011,23,4270；b)J.-B.Fan,Y.Song,S.Wang,J.Meng,G.Yang,X.Guo,L.Feng, L.Jiang,Advanced Functional Materials 2015,25,5368.
[35]C.Teng,S.Wang,X.Lu,J.Wang,G.Ren,Y.Zhu,L.Jiang,Soft Matter 2015, 11,4290.
[36]P.Ilg,Soft Matter 2013,9,3465.

Claims (8)

1. a kind of biological brake, the biological brake is compound including elastin laminin composite crystal glue-Iron oxide magnetic nanoparticles Material, the elastin laminin composite crystal glue-Iron oxide magnetic nanoparticles composite includes elastin laminin composite crystal glue and negative The Iron oxide magnetic nanoparticles on the brilliant glue are loaded in, wherein the elastin laminin composite crystal glue includes 30-60 parts by weight The CNT of methacrylated elastin laminin, the methacrylated gelatin of 30-80 parts by weight and 10-80 parts by weight, institute Stating elastin laminin composite crystal glue also includes stabilizer, and the stabilizer is amphipathic copolymer.
2. biology brake as claimed in claim 1, wherein the stabilizer is polyoxyethylene-poly-oxypropylene polyoxyethylene The amphipathic copolymer of three block.
3. biology brake as claimed in claim 1, wherein the elastin laminin composite crystal glue-Iron oxide magnetic nanoparticles Composite also includes the polypyrrole being carried on the composite.
4. biology brake as claimed in claim 1, wherein the elastin laminin composite crystal glue-Iron oxide magnetic nanoparticles Composite is prepared by the following method：
(a) by methacrylated elastin laminin, methacrylated gelatin, CNT, Iron oxide magnetic nanoparticles and Stabilizer is mixed in aqueous；
(b) polymerization initiator is added into said mixture at low temperature, mixture is crosslinked；
(c) solidify at low temperature products therefrom in step (b), to form the elastin laminin composite crystal glue-iron oxide magnetic Nano particle composite material.
5. biology brake as claimed in claim 4, wherein methods described also includes：
Composite obtained by step (c) is soaked in pyrroles's aqueous solution, and adds the second polymerization initiator, so that pyrroles is single Body polymerize, and in-situ deposition is carried on disperseing on the composite on the supporting structure of the composite to be formed Polypyrrole aggregation.
6. biology brake as claimed in claim 1, wherein the biological brake is circuit changing switch.
7. biology brake as claimed in claim 1, when magnetic field application thereon when, the biological brake turns from open mode Closure state is changed to, or open mode is transformed into from closure state.
8. a kind of circuit, it includes power supply, indicator and the biological braking as claimed in claim 1 as circuit changing switch Device.
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Inventor after: Xing Mengqiu

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